US4711872A - Catalyst for combustion and process for producing same - Google Patents

Catalyst for combustion and process for producing same Download PDF

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Publication number
US4711872A
US4711872A US06/855,484 US85548486A US4711872A US 4711872 A US4711872 A US 4711872A US 85548486 A US85548486 A US 85548486A US 4711872 A US4711872 A US 4711872A
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Prior art keywords
catalyst
barium
compound
combustion
carrier
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US06/855,484
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English (en)
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Yasuyoshi Kato
Nobue Teshima
Masao Ohta
Kunihiko Konishi
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Mitsubishi Hitachi Power Systems Ltd
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Babcock Hitachi KK
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Assigned to BABCOCK-HITACHI KABUSHIKI KAISHA reassignment BABCOCK-HITACHI KABUSHIKI KAISHA ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: KATO, YASUYOSHI, KONISHI, KUNIHIKO, OHTA, MASAO, TESHIMA, NOBUE
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium

Definitions

  • This invention relates to a catalyst for combustion and a process for producing the same. Particularly it relates to a catalyst carrier which hardly causes a reduction in activity and retains a high specific surface area at high temperatures, and a process for producing the same.
  • the factors governing the heat resistance of catalysts vary depending on the catalyst, but in the case of a catalyst having an active ingredient supported on a carrier, the heat stabilities of the carrier and the active ingredient govern the heat resistance. Particularly in the case of a catalyst used at temperatures exceeding 1,000° C., it is indispensable for enhancing the heat resistance that the carrier hardly sinters and can retain a high specific surface area at high temperatures.
  • various inventions directed to oxides which are stable at high temperatures that is, carriers having a high melting point and a specific surface area have been made.
  • ZrO 2 stabilized zirconia
  • composite oxides such as mullite (2Al 2 O 3 .3SiO 2 ), spinel (MgAl 2 O 4 ), La-containing ⁇ -Al 2 O 3 , etc.
  • Japanese patent application Ser. No. Sho 59-92866/1984 Japanese patent application Ser. No. Sho 59-92866/1984.
  • any of these carriers are difficult to regard as having those characteristics necessary to obtain a high performance catalyst.
  • zirconia, mullite, etc. have a tendency that when they are kept at high temperatures of 1,000° C. or higher for a long time, their specific surface areas lower gradually.
  • La-containing ⁇ -Al 2 O 3 has superior properties of retaining a high specific surface area at high temperatures, but lanthanum compounds are expensive as raw materials, and moreover there is a problem that unless it is prepared from an aqueous solution of a lanthanum salt and an aluminum salt according to a complicated coprecipitation method, its characteristic cannot be fully exhibited.
  • the object of the present invention is to provide a high performance catalyst for combustion having overcome the above-mentioned drawbacks of the prior art and having a cheap and heat-resistant carrier capable of retaining a high specific surface area even when it is used at high temperatures of 1,000° C. or higher for a long time, and a process for producing the same.
  • the present inventors have made extensive research on a heat-resistant catalyst carrier based on aluminum compounds, and as a result have found that a carrier obtained by converting a portion or the total of alumina into a compound expressed by a composition formula of BaAl 12 O 19 causes no change in physical properties even at high temperatures such as 1,200° C. or higher and retains a high specific surface area.
  • the present invention resides in a heat-resistant catalyst comprising a compound expressed by a composition formula of BaAl 12 O 19 according to a structural analysis through X-ray diffraction or the like.
  • the catalyst of the present invention has no particular limitation to the raw materials used in its preparation, and those may be sufficient which are identified to have BaAl 12 O 19 formed therein according to a structural analysis such as X-ray diffraction.
  • those which contain a compound of BaAl 12 O 19 under conditions in which the carrier and catalyst are used fall within the scope of the present invention.
  • BaAl 12 O 19 functions not only as carrier but also as catalyst, this, of course, falls within the scope of the present invention.
  • FIG. 1 shows a graph illustrating the specific surface area relative to the quantity of Ba added, of the catalyst carrier used in examples of the present invention.
  • FIG. 2 shows graphs illustrating a comparison of the specific surface area of the catalyst carrier after high temperature treatment of Example 3 with those of Comparative examples.
  • FIG. 3 shows X-ray diffraction patterns of the catalyst carriers of Example 3 and Comparative examples.
  • the heat-resistant catalyst of the present invention is produced by adding a barium compound such as barium nitrate, barium hydroxide, barium acetate, etc. to ⁇ -alumina or an aluminum compound which is converted into ⁇ -alumina by calcination, according to an impregnation method or a kneading method, followed by drying and calcining.
  • a barium compound such as barium nitrate, barium hydroxide, barium acetate, etc.
  • the catalyst of the present invention is produced by adding a water-soluble barium salt and water to ⁇ -alumina or aluminum hydroxide, followed by kneading the mixture, or by impregnating a molded product of ⁇ -alumina with a solution of a water-soluble barium salt dissolved in water, followed by drying and calcining.
  • barium salt barium nitrate (Ba(NO 3 ) 2 ), barium acetate (Ba(CH 3 COO) 2 ), barium hydroxide (Ba(OH) 2 .8H 2 O), etc.
  • quantity of the barium compound added is preferred to be chosen so that the atomic ratio of Al/Ba may be in the range of 100/1 to 100/15, and as to the calcination, by carrying out calcination of 1,000° C. or higher, preferably at 1,200° C. or higher, it is possible to reduce change in physical properties at high temperatures.
  • Barium acetate (Ba(CH 3 COO) 2 ) was mixed with ⁇ -Al 2 O 3 powder having an average diameter of 3 ⁇ so as to give a ratio of Al/Ba of 100/1, 100/3, 100/5, 100/10 or 100/15, followed by adding water (30 ml), kneading the mixture with a mortar, drying the resulting paste at 180° C., thereafter, grinding the dried material to a size of 60 mesh or less, molding it into a cylindrical product of 5 mm ⁇ 5 mmL by means of a press, placing the molded product in a platinum crucible and calcining it 1,200° C. for 2 hours.
  • a carrier was prepared in the same manner as in Example 3.
  • FIG. 2 shows changes in the respective specific surface areas of the carriers of Example 3 and Comparative examples 1 and 2, further subjected to heat treatment at 1200° C., 1300° C. or 1400° C. for 2 hours.
  • the carrier of the present invention is a superior one which can retain the specific surface area of 10 m 2 /g or more up to 1400° C., as compared with the carriers of Comparative examples.
  • FIG. 3 shows X-ray diffraction patterns of these carriers, and in the case of the Ba-added carrier of the present invention, only a broad peak of BaAl 12 O 19 is observed; thus it was found that the main component of the carrier was of fine BaAl 12 O 19 as compound.
  • the carrier of the present invention even after it is heat-treated at 1400° C., the peaks of BaAl 12 O 19 do not become sharp and hence the carrier is judged to have a fine particle diameter, whereas in the case of Comparative example 1, when heat treatment is carried out at a temperature of 1200° C. or higher, and in the case of Comparative example 2, when heat treatment is carried out at 1,400° C., sharp peaks of ⁇ -Al 2 O 3 or La 2 O 3 .11Al 2 O 3 are observed; thus it is seen that in both the cases, sintering occurs and particles grow at high temperatures. From the above results, it is certain that the reason that the carrier of the present invention is stable at high temperatures is due to the presence of a compound of BaAl 12 O 19 having a superior heat stability; this evidences the validity of the present invention.
  • the respective carriers of Examples 1 ⁇ 5 and Comparative examples 1 and 2 were impregnated with an aqueous solution of palladium nitrate (Pd concentration: 13 mg/ml) (12 ml), followed by drying at 180° C. and calcining at 1,200° C. to obtain catalysts. Further, in order to evaluate the heat resistance of the thus obtained catalysts, they were subjected to heat treatment in air at 1,200° C. for 200 hours or at 1,400° C. for 2 hours.
  • any of the catalysts of the present invention exhibited a higher combustion activity than those of Comparative examples 3 and 4, and particularly in the case of the carriers of Examples 7 to 9 having an atomic ratio of Al/Ba of 100/3 to 100/10, a high activity was obtained. This corresponds well to the specific surface areas of carriers shown in FIG. 1; thus it can be seen that the carrier and catalyst of the present invention are superior. Further, it can be seen that the catalysts of Examples 8 to 10 show extremely small reductions in the activity due to heat treatment at 1,200° C. for 200 hours or at 1,400° C. for 2 hours, as compared with the catalysts of Comparative Example 4; thus it can be seen that the catalysts of the present invention are superior as a heat-resistant catalyst for combustion.
  • the catalyst carrier of the present invention can retain a high specific surface area of e.g. 20 m 2 /g or more after heat treatment at 1,200° C. and 10 m 2 /g or more even after heat treatment at 1,400° C., and also can improve the activity of catalysts used at high temperatures to a large extent. Further, even when the catalyst having Pd supported on the present carrier is exposed to a temperature of 1,200° C. or higher, the combustion activity hardly diminishes to make a high load catalyst combustion possible. Still further, cheap ⁇ -Al 2 O 3 and barium compounds can be used as raw materials, and also conventional kneading process or impregnation process can be employed for the preparation; hence it is possible to reduce the production cost of the carrier.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Gas Burners (AREA)
US06/855,484 1985-04-25 1986-04-24 Catalyst for combustion and process for producing same Expired - Lifetime US4711872A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP60089196A JPS61245844A (ja) 1985-04-25 1985-04-25 燃焼用触媒担体およびその製法
JP60-89196 1985-04-25

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JP (1) JPS61245844A (fr)
CA (1) CA1265119A (fr)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0360445A1 (fr) * 1988-09-09 1990-03-28 Catalysts and Chemicals Inc, Far East Catalyseur de reformage d'hydrocarbures à la vapeur d'eau et sa méthode de préparation
US4959339A (en) * 1988-04-13 1990-09-25 Catalysts And Chemicals Inc. Heat-resistant noble metal catalyst and method of producing the same
US4977128A (en) * 1987-12-29 1990-12-11 Babcock-Hitachi Kabushiki Kaisha Catalyst for combustion and process for producing same
EP0461949A1 (fr) * 1990-06-13 1991-12-18 Rhone-Poulenc Chimie Composition à base d'alumine dopée par des terres rares et/ou alcalino-terreux et procédé de fabrication
US5183401A (en) * 1990-11-26 1993-02-02 Catalytica, Inc. Two stage process for combusting fuel mixtures
US5232357A (en) * 1990-11-26 1993-08-03 Catalytica, Inc. Multistage process for combusting fuel mixtures using oxide catalysts in the hot stage
WO1993017968A1 (fr) * 1992-03-12 1993-09-16 Vista Chemical Company Preparation d'alumine stabilisee presentant une resistance accrue a la perte de superficie aux temperatures elevees
US5281128A (en) * 1990-11-26 1994-01-25 Catalytica, Inc. Multistage process for combusting fuel mixtures
US5348717A (en) * 1993-05-11 1994-09-20 Exxon Research & Engineering Co. Synthesis gas from particulate catalysts, and admixtures of particulate catalysts and heat transfer solids
US5593654A (en) * 1992-03-12 1997-01-14 Condea Vista Company Preparation of stabilized alumina having enhanced resistance to loss of surface area at high temperatures
US5837634A (en) * 1992-11-12 1998-11-17 Condea Vista Company Process for producing stabilized alumina having enhanced resistance to loss of surface area at high temperatures
US20090108238A1 (en) * 2007-10-31 2009-04-30 Sud-Chemie Inc. Catalyst for reforming hydrocarbons
US20090118119A1 (en) * 2007-11-01 2009-05-07 Sud-Chemie Inc. Water gas shift catalyst
US20090232728A1 (en) * 2008-03-14 2009-09-17 Sud-Chemie Inc. Ultra high temperature shift catalyst with low methanation
US20100292076A1 (en) * 2009-05-18 2010-11-18 Sud-Chemie Inc. Ultra high temperature shift catalyst with low methanation
US9192917B2 (en) 2010-07-08 2015-11-24 Mitsui Mining & Smelting Co., Ltd. Exhaust gas purifying catalyst and production method for same

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2886867B2 (ja) * 1988-08-26 1999-04-26 バブコツク日立株式会社 触媒担体の製造法
KR20000039382A (ko) * 1998-12-12 2000-07-05 신현준 고온 코크스로 연소실의 연소용 열저항 촉매 담체 제조방법 및이로부터 제조된 촉매 담체

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3988259A (en) * 1975-03-20 1976-10-26 Phillips Petroleum Company Catalyst regeneration
JPS55104652A (en) * 1979-02-05 1980-08-11 Tokyo Roki Kk Catalyst for purifying exhaust from internal combustion engine
US4461919A (en) * 1978-10-10 1984-07-24 The B. F. Goodrich Company Process for the oxychlorination of an alkane using a solid solution catalyst containing iron cations
JPS60238146A (ja) * 1984-05-11 1985-11-27 Hitachi Ltd 耐熱性担体組成物

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2422172A (en) * 1942-07-28 1947-06-10 Shell Dev Thermostable catalysts for the dehydrogenation of hydrocarbons
US3291564A (en) * 1962-08-31 1966-12-13 Exxon Research Engineering Co Method of treating exhaust gases of internal combustion engines utilizing a stabilized alumina catalyst support
US4438219A (en) * 1981-10-28 1984-03-20 Texaco Inc. Alumina catalyst stable at high temperatures

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3988259A (en) * 1975-03-20 1976-10-26 Phillips Petroleum Company Catalyst regeneration
US4461919A (en) * 1978-10-10 1984-07-24 The B. F. Goodrich Company Process for the oxychlorination of an alkane using a solid solution catalyst containing iron cations
JPS55104652A (en) * 1979-02-05 1980-08-11 Tokyo Roki Kk Catalyst for purifying exhaust from internal combustion engine
JPS60238146A (ja) * 1984-05-11 1985-11-27 Hitachi Ltd 耐熱性担体組成物

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4977128A (en) * 1987-12-29 1990-12-11 Babcock-Hitachi Kabushiki Kaisha Catalyst for combustion and process for producing same
US4959339A (en) * 1988-04-13 1990-09-25 Catalysts And Chemicals Inc. Heat-resistant noble metal catalyst and method of producing the same
EP0360445A1 (fr) * 1988-09-09 1990-03-28 Catalysts and Chemicals Inc, Far East Catalyseur de reformage d'hydrocarbures à la vapeur d'eau et sa méthode de préparation
US4988661A (en) * 1988-09-09 1991-01-29 Catalysts And Chemicals Inc., Far East Steam reforming catalyst for hydrocarbons and method of producing the catalyst
EP0461949A1 (fr) * 1990-06-13 1991-12-18 Rhone-Poulenc Chimie Composition à base d'alumine dopée par des terres rares et/ou alcalino-terreux et procédé de fabrication
FR2663245A1 (fr) * 1990-06-13 1991-12-20 Rhone Poulenc Chimie Composition a base d'alumine pour catalyseur et procede de fabrication.
US5397758A (en) * 1990-06-13 1995-03-14 Rhone-Poulenc Chimie Alumina-based compositions and catalysts having high specific surface area
US5183401A (en) * 1990-11-26 1993-02-02 Catalytica, Inc. Two stage process for combusting fuel mixtures
US5281128A (en) * 1990-11-26 1994-01-25 Catalytica, Inc. Multistage process for combusting fuel mixtures
US5232357A (en) * 1990-11-26 1993-08-03 Catalytica, Inc. Multistage process for combusting fuel mixtures using oxide catalysts in the hot stage
WO1993017968A1 (fr) * 1992-03-12 1993-09-16 Vista Chemical Company Preparation d'alumine stabilisee presentant une resistance accrue a la perte de superficie aux temperatures elevees
US5593654A (en) * 1992-03-12 1997-01-14 Condea Vista Company Preparation of stabilized alumina having enhanced resistance to loss of surface area at high temperatures
US5837634A (en) * 1992-11-12 1998-11-17 Condea Vista Company Process for producing stabilized alumina having enhanced resistance to loss of surface area at high temperatures
US5348717A (en) * 1993-05-11 1994-09-20 Exxon Research & Engineering Co. Synthesis gas from particulate catalysts, and admixtures of particulate catalysts and heat transfer solids
US20090108238A1 (en) * 2007-10-31 2009-04-30 Sud-Chemie Inc. Catalyst for reforming hydrocarbons
US20090118119A1 (en) * 2007-11-01 2009-05-07 Sud-Chemie Inc. Water gas shift catalyst
US20090232728A1 (en) * 2008-03-14 2009-09-17 Sud-Chemie Inc. Ultra high temperature shift catalyst with low methanation
US8119558B2 (en) 2008-03-14 2012-02-21 Süd-Chemie Inc. Ultra high temperature shift catalyst with low methanation
US20100292076A1 (en) * 2009-05-18 2010-11-18 Sud-Chemie Inc. Ultra high temperature shift catalyst with low methanation
US9192917B2 (en) 2010-07-08 2015-11-24 Mitsui Mining & Smelting Co., Ltd. Exhaust gas purifying catalyst and production method for same

Also Published As

Publication number Publication date
JPH0557022B2 (fr) 1993-08-23
JPS61245844A (ja) 1986-11-01
CA1265119A (fr) 1990-01-30

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